EP0320081A2 - Procédé de production d'un bain d'électroplacage d'un alliage binaire d'étain-cobalt, d'étain-nickel, ou d'étain-plomb et bain d'électroplacage produit ainsi - Google Patents

Procédé de production d'un bain d'électroplacage d'un alliage binaire d'étain-cobalt, d'étain-nickel, ou d'étain-plomb et bain d'électroplacage produit ainsi Download PDF

Info

Publication number
EP0320081A2
EP0320081A2 EP88305646A EP88305646A EP0320081A2 EP 0320081 A2 EP0320081 A2 EP 0320081A2 EP 88305646 A EP88305646 A EP 88305646A EP 88305646 A EP88305646 A EP 88305646A EP 0320081 A2 EP0320081 A2 EP 0320081A2
Authority
EP
European Patent Office
Prior art keywords
salt
tin
composition
cobalt
range
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP88305646A
Other languages
German (de)
English (en)
Other versions
EP0320081B1 (fr
EP0320081A3 (en
Inventor
Kazuhiro Fukuoka
Haruo Konishi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kosaku and Co Ltd
Original Assignee
Kosaku and Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kosaku and Co Ltd filed Critical Kosaku and Co Ltd
Publication of EP0320081A2 publication Critical patent/EP0320081A2/fr
Publication of EP0320081A3 publication Critical patent/EP0320081A3/en
Application granted granted Critical
Publication of EP0320081B1 publication Critical patent/EP0320081B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys

Definitions

  • This invention relates to a method for production of tin-cobalt, tin-nickel, or tin-lead binary alloy electroplating bath composition and an electroplating bath produced thereby which produces a tin-cobalt, tin-nickel, or tin-lead binary alloy coating glossy and excellent in decorative effect and permits stable plating work.
  • alloy coatings can be used only for thin decorative coatings, though they possess as high corrosionproofness as Monel Metal or Inconel.
  • tin-lead alloy electrodepositing baths As tin-lead alloy electrodepositing baths, a borofluoride bath, a pyrophosphoric acid bath, etc. are available. These methods have problems relating the safety of the workers and are apt to cause water pollution. Moreover, the bath compositions are susceptible of degeneration due to oxidation because they use divalent tin.
  • the inventors continued a study with a view to developing a plating method which is free from the drawbacks of such conventional methods as described above and is capable of producing a glossy coating without reference to thickness. So far they have secured Japanese Patent No. 1,027,262 for an invention characterized by containing 1-hydroxyethane-1,1-phosphoric ester or a salt thereof in a plating bath, Japanese Patent No. 1,027,292 for an invention characterized by further containing aldehyde and a betaine compound, and Japanese Patent No. 1,166,434 and No. 1,180,236 for an invention characterized by containing glycol ether.
  • Coatings of tin-cobalt, tin-nickel, and tin-lead alloys are used in various kinds of articles.
  • a need has arisen for a coating of rich gloss and high decorative value.
  • a plating bath capable of stably forming a coating of desired composition.
  • a plating bath incorporating therein a mixture of 1-hydroxyethane-1,1-diphosphoric acid or a salt thereof with methanesulfonic acid or an alkali salt thereof permits a notable addition to the decorative value of a coating and that a bath using a stannic salt as a tin salt permits the plating work to be performed stably and easily.
  • the present invention has been perfected on the basis of this knowledge.
  • this invention is directed to a method for the production of a tin-cobalt, tin-nickel, or tin-lead binary alloy electroplating bath composition, characterized by mixing (a) a tin salt and at least one member selected from the group consisting of a cobalt salt, a nickel salt, and a lead salt as alloy coating-forming agents, (b) at least one member selected from the group consisting of 1-hydroxyethane-1,1- diphosphoric acid and salts thereof, (c) at least one member selected from the group consisting of methanesulfonic acid and alkali salts thereof and (d) at least one electroconductive salt, and to a tin-cobalt, tin-nickel, or tin-lead binary alloy electroplating bath composition characterized by containing the components mentioned above and produced by the method described above.
  • the plating bath of this invention prevents otherwise possible change of the tin concentration therein due to oxidation and enables the component metals of the plating alloy, namely tin-cobalt, tin-nickel, or tin-lead, placed therein to be simultaneously chelated so that the ratio of metal concentrations in the bath coincides with that in the alloy coating to be formed by plating.
  • composition of the alloy coating formed by electrodeposition therefore, can be easily managed by maintaining the ratio of metal concentrations in the bath within a fixed range.
  • the plating bath of this invention naturally contains such a known electroconductive salt as sodium chloride, potassium chloride, potassium sulfate, sodium sulfate, or ammonium sulfate which is indispensable to the operation of electrodeposition.
  • the amount of this electroconductive salt to be added is in the generally accepted range of 15 to 80 g/liter. If the amount of this salt is unduly large, the excess salt can cause coating defects such as surface streaks. If the amount is unduly small, the bath has high electric resistance.
  • the bath composition of the present invention is produced by mixing the aforementioned four components (a), (b), (c) and (d).
  • the coating produced by the electroplating using this bath composition possesses heretofore unattainable excellent metallic gloss.
  • the electroplating bath of the present invention when necessary, may incorporate other components therein to the extent extent that the bath composition is not adversely affected by the added components.
  • the plating operation using the electroplating bath of this invention is desired to be carried out under conditions such that the bath temperature falls in the range of 50 to 65 C, the current density at the cathode in the range of 0.5 to 5 A/dm 2 , and the current density at the anode in the range of 0.5 to 2.5 A/dm 2 .
  • the pH value of the plating bath can be selected within a very wide range of 3 to 13.5.
  • the anode may be an ordinary insoluble anode of carbon or ferrite.
  • a variable anode may be also used.
  • an anode made of the same substance as the coating-forming substance, i.e. tin, cobalt, or nickel may be used.
  • the plating is effected by using an anode made of tin, partitioning the interior of the bath with a cation-exchange membrane, allowing stannous ion dissolving out of the anode to be oxidized into stannic ion, and passing the stannic ion through a diaphragm into the bath.
  • the coating-forming substance to be replenished with the progress of the plating operation may be limited to the other member of the coating-forming agent than the tin salt.
  • the control of both compositions is very easy.
  • the time of electrolysis was 2 to 4 minutes for the plating with the tin-cobalt alloy or with the tin-nickel alloy and 5 to 10 minutes for the plating with the tin-lead alloy.
  • the adhesion test was carried out in accordance with the method of JIS H8504, 3-8-a, with the results rated on a three-point scale, wherein o stands for absence of separation, A for 5% separation, and x for 10% separation.
  • the results of the test for resistance to nitric acid, the test for resistance to hydrochloric acid, and the test for resistance to an alkali etchant were rated on a three-point scale, wherein o stands for absence of change, A for slight change, and x for appreciable change respectively in alloy coating after immersion.
  • the results of the test for gloss were rated on a three-point scale, wherein @ stands for conspicuous gloss, o for ordinary gloss, and X for rather poor gloss.
  • the electroplating bath composition of the present invention contains 1-hydroxyethane-1,1-diphosphoric acid or salt thereof and methanesulfonic acid or an alkali salt thereof as mixed and the coating produced by the electroplating using the composition bath is stable and excellent in gloss.
  • the plating operation proceeds without formation of any precipitation due to such a rapid oxidation reaction as Sn 2+ - Sn 4+ + 2e which would occur if a stannous acid were used, the plating bath has a stable tin concentration, and the plating operation can be effectively carried out stably at a pH value selected within a wide range from acidic bath to alkaline bath.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
EP88305646A 1987-12-05 1988-06-21 Procédé de production d'un bain d'électroplacage d'un alliage binaire d'étain-cobalt, d'étain-nickel, ou d'étain-plomb et bain d'électroplacage produit ainsi Expired - Lifetime EP0320081B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP306851/87 1987-12-05
JP62306851A JPH01149987A (ja) 1987-12-05 1987-12-05 スズ−コバルト、スズ−ニッケル、スズ−鉛二元合金電気めっき浴組成物

Publications (3)

Publication Number Publication Date
EP0320081A2 true EP0320081A2 (fr) 1989-06-14
EP0320081A3 EP0320081A3 (en) 1990-03-28
EP0320081B1 EP0320081B1 (fr) 1992-10-07

Family

ID=17962014

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88305646A Expired - Lifetime EP0320081B1 (fr) 1987-12-05 1988-06-21 Procédé de production d'un bain d'électroplacage d'un alliage binaire d'étain-cobalt, d'étain-nickel, ou d'étain-plomb et bain d'électroplacage produit ainsi

Country Status (8)

Country Link
US (1) US4828657A (fr)
EP (1) EP0320081B1 (fr)
JP (1) JPH01149987A (fr)
KR (1) KR910004972B1 (fr)
CA (1) CA1316484C (fr)
DE (1) DE3875227T2 (fr)
HK (1) HK106493A (fr)
SG (1) SG65193G (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6309760B1 (en) 1998-10-27 2001-10-30 Dana Corporation Bearing material

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0713299B2 (ja) * 1990-10-22 1995-02-15 株式会社コサク 無電解はんだめっき浴組成物
US6015482A (en) * 1997-12-18 2000-01-18 Circuit Research Corp. Printed circuit manufacturing process using tin-nickel plating
US6562220B2 (en) 1999-03-19 2003-05-13 Technic, Inc. Metal alloy sulfate electroplating baths
US6179985B1 (en) 1999-03-19 2001-01-30 Technic, Inc. Metal alloy fluoroborate electroplating baths
US6251253B1 (en) 1999-03-19 2001-06-26 Technic, Inc. Metal alloy sulfate electroplating baths
US6248228B1 (en) 1999-03-19 2001-06-19 Technic, Inc. And Specialty Chemical System, Inc. Metal alloy halide electroplating baths
US6183619B1 (en) 1999-03-19 2001-02-06 Technic, Inc. Metal alloy sulfonic acid electroplating baths
GB0106131D0 (en) * 2001-03-13 2001-05-02 Macdermid Plc Electrolyte media for the deposition of tin alloys and methods for depositing tin alloys
FR2832160B1 (fr) * 2001-11-15 2005-01-14 Atofina PROCEDE DE TRAVAIL OU MISE EN FORME DES METAUX EN PRESENCE DE LUBRIFIANTS AQUEUX A BASE D'ACIDE METHANESULFONIQUE (AMS) ou D'UN SEL HYDROSOLUBLE D'AMS
US7195702B2 (en) * 2003-06-06 2007-03-27 Taskem, Inc. Tin alloy electroplating system
US20110226613A1 (en) 2010-03-19 2011-09-22 Robert Rash Electrolyte loop with pressure regulation for separated anode chamber of electroplating system
US9404194B2 (en) 2010-12-01 2016-08-02 Novellus Systems, Inc. Electroplating apparatus and process for wafer level packaging
US9534308B2 (en) 2012-06-05 2017-01-03 Novellus Systems, Inc. Protecting anodes from passivation in alloy plating systems
JP2021501268A (ja) 2017-11-01 2021-01-14 ラム リサーチ コーポレーションＬａｍ Ｒｅｓｅａｒｃｈ Ｃｏｒｐｏｒａｔｉｏｎ 電気化学メッキ装置におけるメッキ電解液濃度の制御

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53141130A (en) * 1977-05-16 1978-12-08 Kosaku Kk Plating bath component
EP0128358A1 (fr) * 1983-05-13 1984-12-19 Mitsubishi Kasei Corporation Produit lustré d'apparence bronzée
EP0207732A1 (fr) * 1985-06-26 1987-01-07 Mcgean-Rohco, Inc. Bain de placage et méthode de dépôt électrolytique d'étain et/ou de plomb
EP0216955A1 (fr) * 1985-09-20 1987-04-08 LeaRonal, Inc. Procédé pour la préparation d'une solution électrolytique pour le dépôt d'étain ou des alliages étain-plomb

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52106331A (en) * 1976-03-05 1977-09-06 Kosaku Kk Plating bath
JPS61117297A (ja) * 1984-11-13 1986-06-04 Ebara Yuujiraito Kk スズ属金属めつき液

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53141130A (en) * 1977-05-16 1978-12-08 Kosaku Kk Plating bath component
EP0128358A1 (fr) * 1983-05-13 1984-12-19 Mitsubishi Kasei Corporation Produit lustré d'apparence bronzée
EP0207732A1 (fr) * 1985-06-26 1987-01-07 Mcgean-Rohco, Inc. Bain de placage et méthode de dépôt électrolytique d'étain et/ou de plomb
EP0216955A1 (fr) * 1985-09-20 1987-04-08 LeaRonal, Inc. Procédé pour la préparation d'une solution électrolytique pour le dépôt d'étain ou des alliages étain-plomb

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6309760B1 (en) 1998-10-27 2001-10-30 Dana Corporation Bearing material
US6472086B2 (en) 1998-10-27 2002-10-29 Dana Corporation Bearing material

Also Published As

Publication number Publication date
JPH049875B2 (fr) 1992-02-21
EP0320081B1 (fr) 1992-10-07
HK106493A (en) 1993-10-15
US4828657A (en) 1989-05-09
CA1316484C (fr) 1993-04-20
JPH01149987A (ja) 1989-06-13
EP0320081A3 (en) 1990-03-28
SG65193G (en) 1993-08-06
DE3875227D1 (de) 1992-11-12
KR910004972B1 (ko) 1991-07-20
DE3875227T2 (de) 1993-03-18
KR890010287A (ko) 1989-08-07

Similar Documents

Publication Publication Date Title
US4428802A (en) Palladium-nickel alloy electroplating and solutions therefor
EP0320081B1 (fr) Procédé de production d'un bain d'électroplacage d'un alliage binaire d'étain-cobalt, d'étain-nickel, ou d'étain-plomb et bain d'électroplacage produit ainsi
US20060283714A1 (en) Gold alloy electrolytes
US4163700A (en) Method for stabilizing tin or tin alloy electroplating baths
JPH02107794A (ja) 白金または白金合金の電気めっき浴および電気めっき方法
TWI439580B (zh) 用於電鍍錫合金層之焦磷酸鹽基浴
US4242180A (en) Ammonia free palladium electroplating bath using aminoacetic acid
US4076598A (en) Method, electrolyte and additive for electroplating a cobalt brightened gold alloy
US4715935A (en) Palladium and palladium alloy plating
US2658032A (en) Electrodeposition of bright copper-tin alloy
US4299672A (en) Bath and process for galvanic separation of palladium-nickel alloys
US4366035A (en) Electrodeposition of gold alloys
US4297177A (en) Method and composition for electrodepositing palladium/nickel alloys
US4478692A (en) Electrodeposition of palladium-silver alloys
US4673471A (en) Method of electrodepositing a chromium alloy deposit
US4048023A (en) Electrodeposition of gold-palladium alloys
GB2046794A (en) Silver and gold/silver alloy plating bath and method
US4465563A (en) Electrodeposition of palladium-silver alloys
US4297179A (en) Palladium electroplating bath and process
US3729396A (en) Rhodium plating composition and method for plating rhodium
US4634505A (en) Process and bath for the electrolytic deposition of gold-tin alloy coatings
EP0018752A1 (fr) Dépôt électrolytique d'un alliage d'or blanc, sa préparation et bain électrolytique
US4778574A (en) Amine-containing bath for electroplating palladium
US4411744A (en) Bath and process for high speed nickel electroplating
US4253920A (en) Composition and method for gold plating

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): DE FR GB

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): DE FR GB

17P Request for examination filed

Effective date: 19900321

17Q First examination report despatched

Effective date: 19910704

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB

REF Corresponds to:

Ref document number: 3875227

Country of ref document: DE

Date of ref document: 19921112

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20000526

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20010622

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20010625

Year of fee payment: 14

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020403

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020621

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20020621

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030228

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST